Dipole Interaction-Controlled Stereoselectivity in Aldol Reaction of α-CF3 Enolate with Fluoral

Organic Letters

Volumn 5, Issue 25, 2003, Pages 4807-4809

  Itoh, Yoshimitsu ^a   Yamanaka, Masahiro ^a   Mikami, Koichi ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; FLUORIDE SODIUM; FLUORINE DERIVATIVE; KETONE DERIVATIVE;

ALDOL REACTION; ARTICLE; DIPOLE; ELECTRON; MOLECULAR INTERACTION; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0347683361     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0358307     Document Type: Article

References (25)

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2. (b) Gawley, R. E.; Aube, J. Principles of Asymmetric Synthesis; Pergamon: London, 1996.
3. Itoh, Y.; Yamanaka, M.; Mikami, K. Org. Lett. 2003, 5, 4803-4806.
4. Zimmerman, H. E.; Traxler, M. D. J. Am. Chem. Soc. 1957, 79, 1920-1923.
5. All calculations were performed using the Gaussian 98 program package (Gaussian, Inc.: Pittsburgh, PA, 1998).
6. Hehre, W. J.; Radom, L.; von Ragué Schleyer, P.; Pople, J. A. Ab initio Molecular Orbital Theory; Wiley: New York, 1986; see also references therein.
7. (a) Li, Y.; Paddon-Row, M. N.; Houk, K. N. J. Am. Chem. Soc. 1988, 110, 3684-3686.
8. (b) Li, Y.; Paddon-Row, M. N.; Houk, K. N. J. Org. Chem. 1990, 55, 481-493.
9. 3-acetaldehyde and fluoral were also carried out at the B3LYP/631LAN (LANL2DZ for Ti, 6-31G* for others) level. As expected, TS1 was more stable (6.4 kcal/mol) than TS2.
10. 3 = 2.4-2.5 (kcal/mol). Jensen, F. R.; Bushweller, C. H. Adv. Alicycl. Chem. 1971, 3, 139-195.
11. We have carried out the single-point energy calculation with the self-consistent reaction field (SCRF) method based on the polarized continuum model (PCM, ε = 4.355 for ether) at the gas-phase geometry. The result was almost the same (TS1 is 2.3 kcal/mol stable than TS2).
12. With the Ti-amine system, there are many examples that support the formation of (Z)-enolate to give syn-aldol product via a cyclic TS. (a) Harrison. C. R. Tetrahedron Lett. 1987, 28, 4135-4138. (b) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868. (c) Evans, D. A.; Urpí, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216. (d) Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpí, F. J. Am. Chem. Soc. 1991, 113, 1047-1049. (d) Esteve, C.; Ferreró, M.; Romea, P.; Urpí, F.; Vilarrasa, J. Tetrahedron Lett. 1999, 40, 5079-5082. (e) Tanabe, Y.; Matsumoto, N.; Higashi, T.; Misaki, T.; Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron 2002, 58, 8269-8280. (f) Solsona, J. G.; Romea P.; Urpí, F.; Vilarrasa, J. Org. Lett. 2003, 5, 519-522.
13. With the Ti-amine system, there are many examples that support the formation of (Z)-enolate to give syn-aldol product via a cyclic TS. (a) Harrison. C. R. Tetrahedron Lett. 1987, 28, 4135-4138. (b) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868. (c) Evans, D. A.; Urpí, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216. (d) Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpí, F. J. Am. Chem. Soc. 1991, 113, 1047-1049. (d) Esteve, C.; Ferreró, M.; Romea, P.; Urpí, F.; Vilarrasa, J. Tetrahedron Lett. 1999, 40, 5079-5082. (e) Tanabe, Y.; Matsumoto, N.; Higashi, T.; Misaki, T.; Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron 2002, 58, 8269-8280. (f) Solsona, J. G.; Romea P.; Urpí, F.; Vilarrasa, J. Org. Lett. 2003, 5, 519-522.
14. With the Ti-amine system, there are many examples that support the formation of (Z)-enolate to give syn-aldol product via a cyclic TS. (a) Harrison. C. R. Tetrahedron Lett. 1987, 28, 4135-4138. (b) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868. (c) Evans, D. A.; Urpí, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216. (d) Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpí, F. J. Am. Chem. Soc. 1991, 113, 1047-1049. (d) Esteve, C.; Ferreró, M.; Romea, P.; Urpí, F.; Vilarrasa, J. Tetrahedron Lett. 1999, 40, 5079-5082. (e) Tanabe, Y.; Matsumoto, N.; Higashi, T.; Misaki, T.; Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron 2002, 58, 8269-8280. (f) Solsona, J. G.; Romea P.; Urpí, F.; Vilarrasa, J. Org. Lett. 2003, 5, 519-522.
15. With the Ti-amine system, there are many examples that support the formation of (Z)-enolate to give syn-aldol product via a cyclic TS. (a) Harrison. C. R. Tetrahedron Lett. 1987, 28, 4135-4138. (b) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868. (c) Evans, D. A.; Urpí, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216. (d) Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpí, F. J. Am. Chem. Soc. 1991, 113, 1047-1049. (d) Esteve, C.; Ferreró, M.; Romea, P.; Urpí, F.; Vilarrasa, J. Tetrahedron Lett. 1999, 40, 5079-5082. (e) Tanabe, Y.; Matsumoto, N.; Higashi, T.; Misaki, T.; Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron 2002, 58, 8269-8280. (f) Solsona, J. G.; Romea P.; Urpí, F.; Vilarrasa, J. Org. Lett. 2003, 5, 519-522.
16. With the Ti-amine system, there are many examples that support the formation of (Z)-enolate to give syn-aldol product via a cyclic TS. (a) Harrison. C. R. Tetrahedron Lett. 1987, 28, 4135-4138. (b) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868. (c) Evans, D. A.; Urpí, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216. (d) Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpí, F. J. Am. Chem. Soc. 1991, 113, 1047-1049. (d) Esteve, C.; Ferreró, M.; Romea, P.; Urpí, F.; Vilarrasa, J. Tetrahedron Lett. 1999, 40, 5079-5082. (e) Tanabe, Y.; Matsumoto, N.; Higashi, T.; Misaki, T.; Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron 2002, 58, 8269-8280. (f) Solsona, J. G.; Romea P.; Urpí, F.; Vilarrasa, J. Org. Lett. 2003, 5, 519-522.
17. With the Ti-amine system, there are many examples that support the formation of (Z)-enolate to give syn-aldol product via a cyclic TS. (a) Harrison. C. R. Tetrahedron Lett. 1987, 28, 4135-4138. (b) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868. (c) Evans, D. A.; Urpí, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216. (d) Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpí, F. J. Am. Chem. Soc. 1991, 113, 1047-1049. (d) Esteve, C.; Ferreró, M.; Romea, P.; Urpí, F.; Vilarrasa, J. Tetrahedron Lett. 1999, 40, 5079-5082. (e) Tanabe, Y.; Matsumoto, N.; Higashi, T.; Misaki, T.; Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron 2002, 58, 8269-8280. (f) Solsona, J. G.; Romea P.; Urpí, F.; Vilarrasa, J. Org. Lett. 2003, 5, 519-522.
18. With the Ti-amine system, there are many examples that support the formation of (Z)-enolate to give syn-aldol product via a cyclic TS. (a) Harrison. C. R. Tetrahedron Lett. 1987, 28, 4135-4138. (b) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868. (c) Evans, D. A.; Urpí, F.; Somers, T. C.; Clark, J. S.; Bilodeau, M. T. J. Am. Chem. Soc. 1990, 112, 8215-8216. (d) Evans, D. A.; Rieger, D. L.; Bilodeau, M. T.; Urpí, F. J. Am. Chem. Soc. 1991, 113, 1047-1049. (d) Esteve, C.; Ferreró, M.; Romea, P.; Urpí, F.; Vilarrasa, J. Tetrahedron Lett. 1999, 40, 5079-5082. (e) Tanabe, Y.; Matsumoto, N.; Higashi, T.; Misaki, T.; Itoh, T.; Yamamoto, M.; Mitarai, K.; Nishii, Y. Tetrahedron 2002, 58, 8269-8280. (f) Solsona, J. G.; Romea P.; Urpí, F.; Vilarrasa, J. Org. Lett. 2003, 5, 519-522.
19. 3-enolate and its aldol reaction: (a) Nakamura, E.; Shimada, J.; Horiguchi, Y.; Kuwajima, I. Tetrahedron Lett. 1983, 24, 3341-3342. (b) Nakamura, E.; Kuwajima, I. Tetrahedron Lett. 1983, 24, 3343-3346.
20. 3-enolate and its aldol reaction: (a) Nakamura, E.; Shimada, J.; Horiguchi, Y.; Kuwajima, I. Tetrahedron Lett. 1983, 24, 3341-3342. (b) Nakamura, E.; Kuwajima, I. Tetrahedron Lett. 1983, 24, 3343-3346.
21. Typical experimental procedure. To a solution of 1,1,1-trifluoro-4,4- dimethyl-5-phenyl-3-pentanone (1) (48.9 mg, 0.2 mmol) in dichloromethane (2 mL) was added titanium tetrachloride (26.3 μL, 0.24 mmol) at 0°C, and the mixture was stirred for 10 min under an argon atmosphere. Then, the reaction mixture was cooled to -78°C and added tributylamine (66.7 μL, 0.28 mmol) at this temperature. The reaction mixture was stirred for 15 min, and then an excess amount of freshly distilled fluoral was added. After stirring for 4 h at -78°C, the reaction mixture was quenched by adding phosphorous buffer (pH = 7) at this temperature. The mixture was extracted three times with ether. The combined organic layer was washed with brine, dried over anhydrous sodium sulfate, and evaporated under reduced pressure. The crude mixture was purified by silica gel column chromatography (hexane/acetone = 10:1). 5-Hydroxy-2,2-dimethyl-1,5-diphenyl-4-trifluoromethyl-3-pentanone (3, 56.7 mg, 83%) was obtained.
22. 4 to prevent deprotonation at the enolization step.
23. 1H-coupling constant (Jeffery, E. A.; Meisters, A.; Mole, T. J. Organomet. Chem. 1974, 74, 373-384) could not be used because of the small coupling constant of the aldol product (J = 2.8 Hz).
24. Rychnovsky, S. D.; Rogers, B.; Yang, G. J. Org. Chem. 1993, 58, 3511-3515.
25. Mikami, K.; Itoh, Y.; Yamanaka, M. Chem. Rev. 2004, in press.